Metal-Compound-Removing Solvent And Method In Lithography

ABSTRACT

A photoresist layer is coated over a wafer. The photoresist layer includes a metal-containing material. An extreme ultraviolet (EUV) lithography process is performed to the photoresist layer to form a patterned photoresist. The wafer is cleaned with a cleaning fluid to remove the metal-containing material. The cleaning fluid includes a solvent having Hansen solubility parameters of delta D in a range between 13 and 25, delta P in a range between 3 and 25, and delta H in a range between 4 and 30. The solvent contains an acid with an acid dissociation constant less than 4 or a base with an acid dissociation constant greater than 9.

PRIORITY DATA

The present application is a continuation application of U.S. Ser. No.17/121,261, filed Dec. 14, 2020, which is a continuation application ofU.S. Ser. No. 15/351,529, filed Nov. 15, 2016, which claims priority toU.S. Provisional Patent Application Ser. No. 62/371,324, filed on Aug.5, 2016, each of which is hereby incorporated by reference in itsentirety.

BACKGROUND

The semiconductor integrated circuit (IC) industry has experienced rapidgrowth. Technological advances in IC materials and design have producedgenerations of ICs where each generation has smaller and more complexcircuits than the previous generation. However, these advances haveincreased the complexity of processing and manufacturing ICs and, forthese advances to be realized, similar developments in IC processing andmanufacturing are needed. In the course of integrated circuit evolution,functional density (i.e., the number of interconnected devices per chiparea) has generally increased while geometry size (i.e., the smallestcomponent (or line) that can be created using a fabrication process) hasdecreased.

As the semiconductor device sizes continue to shrink, for example below20 nanometer (nm) nodes, traditional lithography technologies haveoptical restrictions, which leads to resolution issues and may notachieve the desired lithography performance. In comparison, extremeultraviolet (EUV) lithography can achieve much smaller device sizes.However, conventional EUV lithography still has some shortcomings, forexample shortcomings with respect to EUV photo absorption and/orcontamination caused by metal-containing materials. As a result,semiconductor fabrication performance may be compromised or degraded.

Therefore, while existing systems and method for performing EUVlithography have been generally adequate for their intended purposes,they have not been entirely satisfactory in every aspect.

BRIEF DESCRIPTION OF THE DRAWINGS

Aspects of the present disclosure are best understood from the followingdetailed description when read with the accompanying figures. It isemphasized that, in accordance with the standard practice in theindustry, various features are not drawn to scale. In fact, thedimensions of the various features may be arbitrarily increased orreduced for clarity of discussion.

FIG. 1 is a schematic view of a lithography system constructed inaccordance with some embodiments of the present disclosure.

FIG. 2 is a sectional view of a EUV mask constructed in accordance withsome embodiments of the present disclosure.

FIG. 3 is a diagrammatic cross-sectional side view of a semiconductorwafer in accordance with some embodiments of the present disclosure.

FIGS. 4-6 illustrate different flows of cleaning a wafer to remove ametal-containing contaminant according to embodiments of the presentdisclosure.

FIG. 7 illustrates an embodiment of a cleaning system for cleaning awafer to remove a metal-containing contaminant according to embodimentsof the present disclosure.

FIGS. 8-9 provide visual illustrations of different flows in which acleaning process is performed according to embodiments of the presentdisclosure.

FIG. 10 is a diagrammatic illustration of various process flowsaccording to embodiments of the present disclosure.

FIG. 11 is a flowchart illustrating a method of fabricating asemiconductor device in accordance with some embodiments of the presentdisclosure.

DETAILED DESCRIPTION

The following disclosure provides many different embodiments, orexamples, for implementing different features of the provided subjectmatter. Specific examples of components and arrangements are describedbelow to simplify the present disclosure. These are, of course, merelyexamples and are not intended to be limiting. For example, the formationof a first feature over or on a second feature in the description thatfollows may include embodiments in which the first and second featuresare formed in direct contact, and may also include embodiments in whichadditional features may be formed between the first and second features,such that the first and second features may not be in direct contact. Inaddition, the present disclosure may repeat reference numerals and/orletters in the various examples. This repetition is for the purpose ofsimplicity and clarity and does not in itself dictate a relationshipbetween the various embodiments and/or configurations discussed.

Further, spatially relative terms, such as “beneath,” “below,” “lower,”“above,” “upper” and the like, may be used herein for ease ofdescription to describe one element or feature's relationship to anotherelement(s) or feature(s) as illustrated in the figures. The spatiallyrelative terms are intended to encompass different orientations of thedevice in use or operation in addition to the orientation depicted inthe figures. The apparatus may be otherwise oriented (rotated 90 degreesor at other orientations) and the spatially relative descriptors usedherein may likewise be interpreted accordingly.

Extreme ultraviolet (EUV) lithography has become widely used due to itsability to achieve small semiconductor device sizes. However,conventional systems and methods of performing EUV lithography may haveshortcomings. For example, conventional photoresist materials aretypically organic materials. These organic materials may not beoptimized for photon absorption in the EUV range. Thus, metal-containingmaterials may be added to photoresist materials for EUV lithography.However, these metal-containing materials may cause potentialcontamination problems. For example, if the metal-containing materialsare not properly washed away or otherwise removed from the EUVphotolithography apparatus or the wafer undergoing EUV lithography, theycould cause contamination for subsequent semiconductor fabricationprocesses where metal is not needed (or desired), or they couldcontaminate other semiconductor fabrication tools as the wafer istransferred between the various semiconductor fabrication tools. Thecontamination due to the metal-containing materials in the EUVphotoresist may therefore cause semiconductor fabrication problemsand/or degrade semiconductor device performance.

To overcome the problems discussed above, the present disclosureprovides a novel solvent and a novel system and method of using thesolvent to effectively clean the metal-containing materials (in EUVphotoresist) off of the wafer. The various aspects of the presentdisclosure will be discussed below in greater detail with reference toFIGS. 1-10 . First, a EUV lithography system will be discussed belowwith reference to FIGS. 1-2 . Next, the details of a cleaning system andmethod according to embodiments of the present disclosure are discussedwith reference to FIGS. 3-10 .

FIG. 1 is a schematic view diagram of a EUV lithography system 10,constructed in accordance with some embodiments. The EUV lithographysystem 10 may also be generically referred to as a scanner that isconfigured to perform lithography exposure processes with respectiveradiation source and exposure mode. The EUV lithography system 10 isdesigned to expose a photoresist layer by EUV light or EUV radiation.The photoresist layer is a material sensitive to the EUV light. The EUVlithography system 10 employs a radiation source 12 to generate EUVlight, such as EUV light having a wavelength ranging between about 1 nmand about 100 nm. In one particular example, the radiation source 12generates a EUV light with a wavelength centered at about 13.5 nm.Accordingly, the radiation source 12 is also referred to as EUVradiation source 12.

The lithography system 10 also employs an illuminator 14. In variousembodiments, the illuminator 14 includes various refractive opticcomponents, such as a single lens or a lens system having multiplelenses (zone plates) or alternatively reflective optics (for EUVlithography system), such as a single mirror or a mirror system havingmultiple mirrors in order to direct light from the radiation source 12onto a mask stage 16, particularly to a mask 18 secured on the maskstage 16. In the present embodiment where the radiation source 12generates light in the EUV wavelength range, the illuminator 14 employsreflective optics. In some embodiments, the illuminator 14 includes adipole illumination component.

In some embodiments, the illuminator 14 is operable to configure themirrors to provide a proper illumination to the mask 18. In one example,the mirrors of the illuminator 14 are switchable to reflect EUV light todifferent illumination positions. In some embodiment, a stage prior tothe illuminator 14 may additionally include other switchable mirrorsthat are controllable to direct the EUV light to different illuminationpositions with the mirrors of the illuminator 14. In some embodiments,the illuminator 14 is configured to provide an on-axis illumination(ONI) to the mask 18. In an example, a disk illuminator 14 with partialcoherence σ being at most 0.3 is employed. In some other embodiments,the illuminator 14 is configured to provide an off-axis illumination(OAI) to the mask 18. In an example, the illuminator 14 is a dipoleilluminator. The dipole illuminator has a partial coherence σ of at most0.3 in some embodiments.

The lithography system 10 also includes a mask stage 16 configured tosecure a mask 18. In some embodiments, the mask stage 16 includes anelectrostatic chuck (e-chuck) to secure the mask 18. This is because gasmolecules absorb EUV light, and the lithography system for the EUVlithography patterning is maintained in a vacuum environment to avoidthe EUV intensity loss. In the disclosure, the terms of mask, photomask,and reticle are used interchangeably to refer to the same item.

In the present embodiment, the lithography system 10 is a EUVlithography system, and the mask 18 is a reflective mask. One exemplarystructure of the mask 18 is provided for illustration. The mask 18includes a substrate with a suitable material, such as a low thermalexpansion material (LTEM) or fused quartz. In various examples, the LTEMincludes TiO₂ doped SiO₂, or other suitable materials with low thermalexpansion.

The mask 18 also includes a reflective ML deposited on the substrate.The ML includes a plurality of film pairs, such as molybdenum-silicon(Mo/Si) film pairs (e.g., a layer of molybdenum above or below a layerof silicon in each film pair). Alternatively, the ML may includemolybdenum-beryllium (Mo/Be) film pairs, or other suitable materialsthat are configurable to highly reflect the EUV light.

The mask 18 may further include a capping layer, such as ruthenium (Ru),disposed on the ML for protection. The mask 18 further includes anabsorption layer deposited over the ML. The absorption layer ispatterned to define a layer of an integrated circuit (IC).Alternatively, another reflective layer may be deposited over the ML andis patterned to define a layer of an integrated circuit, thereby forminga EUV phase shift mask.

The lithography system 10 also includes a projection optics module (orprojection optics box (POB) 20 for imaging the pattern of the mask 18 onto a semiconductor substrate 26 secured on a substrate stage 28 of thelithography system 10. The POB 20 has refractive optics (such as for UVlithography system) or alternatively reflective optics (such as for EUVlithography system) in various embodiments. The light directed from themask 18, diffracted into various diffraction orders and carrying theimage of the pattern defined on the mask, is collected by the POB 20.The POB 20 may include a magnification of less than one (thereby thesize of the “image” on a target (such as target 26 discussed below) issmaller than the size of the corresponding “object” on the mask). Theilluminator 14 and the POB 20 are collectively referred to as an opticalmodule of the lithography system 10.

The lithography system 10 also includes a pupil phase modulator 22 tomodulate optical phase of the light directed from the mask 18 so thatthe light has a phase distribution on a projection pupil plane 24. Inthe optical module, there is a plane with field distributioncorresponding to Fourier Transform of the object (the mask 18 in thepresent case). This plane is referred to as projection pupil plane. Thepupil phase modulator 22 provides a mechanism to modulate the opticalphase of the light on the projection pupil plane 24. In someembodiments, the pupil phase modulator 22 includes a mechanism to tunethe reflective mirrors of the POB 20 for phase modulation. For example,the mirrors of the POB 20 are switchable and are controlled to reflectthe EUV light, thereby modulating the phase of the light through the POB20.

In some embodiments, the pupil phase modulator 22 utilizes a pupilfilter placed on the projection pupil plane 24. A pupil filter filtersout specific spatial frequency components of the EUV light from the mask18. Particularly, the pupil filter is a phase pupil filter thatfunctions to modulate phase distribution of the light directed throughthe POB 20. However, utilizing a phase pupil filter is limited in somelithography system (such as an EUV lithography system) since allmaterials absorb EUV light.

As discussed above, the lithography system 10 also includes thesubstrate stage 28 to secure a target 26 to be patterned, such as asemiconductor substrate. In the present embodiment, the semiconductorsubstrate is a semiconductor wafer, such as a silicon wafer or othertype of wafer. The target 26 is coated with the resist layer sensitiveto the radiation beam, such as EUV light in the present embodiment.Various components including those described above are integratedtogether and are operable to perform lithography exposing processes. Thelithography system 10 may further include other modules or be integratedwith (or be coupled with) other modules.

The mask 18 and the method making the same are further described inaccordance with some embodiments. In some embodiments, the maskfabrication process includes two operations: a blank mask fabricationprocess and a mask patterning process. During the blank mask fabricationprocess, a blank mask is formed by deposing suitable layers (e.g.,reflective multiple layers) on a suitable substrate. The blank mask isthen patterned during the mask patterning process to achieve a desireddesign of a layer of an integrated circuit (IC). The patterned mask isthen used to transfer circuit patterns (e.g., the design of a layer ofan IC) onto a semiconductor wafer. The patterns can be transferred overand over onto multiple wafers through various lithography processes. Aset of masks is used to construct a complete IC.

The mask 18 includes a suitable structure, such as a binary intensitymask (BIM) and phase-shifting mask (PSM) in various embodiments. Anexample BIM includes absorptive regions (also referred to as opaqueregions) and reflective regions, patterned to define an IC pattern to betransferred to the target. In the opaque regions, an absorber ispresent, and an incident light is almost fully absorbed by the absorber.In the reflective regions, the absorber is removed and the incidentlight is diffracted by a multilayer (ML). The PSM can be an attenuatedPSM (AttPSM) or an alternating PSM (AltPSM). An exemplary PSM includes afirst reflective layer (such as a reflective ML) and a second reflectivelayer patterned according to an IC pattern. In some examples, an AttPSMusually has a reflectivity of 2%-15% from its absorber, while an AltPSMusually has a reflectivity of larger than 50% from its absorber.

One example of the mask 18 is shown in FIG. 2 . The mask 18 in theillustrated embodiment is a EUV mask, and includes a substrate 30 madeof a LTEM. The LTEM material may include TiO₂ doped SiO₂, and/or otherlow thermal expansion materials known in the art. In some embodiments, aconductive layer 32 is additionally disposed under on the backside ofthe LTEM substrate 30 for the electrostatic chucking purpose. In oneexample, the conductive layer 32 includes chromium nitride (CrN), thoughother suitable compositions are possible.

The EUV mask 18 includes a reflective multilayer (ML) structure 34disposed over the LTEM substrate 30. The ML structure 34 may be selectedsuch that it provides a high reflectivity to a selected radiationtype/wavelength. The ML structure 34 includes a plurality of film pairs,such as Mo/Si film pairs (e.g., a layer of molybdenum above or below alayer of silicon in each film pair). Alternatively, the ML structure 34may include Mo/Be film pairs, or any materials with refractive indexdifference being highly reflective at EUV wavelengths.

Still referring to FIG. 2 , the EUV mask 18 also includes a cappinglayer 36 disposed over the ML structure 34 to prevent oxidation of theML. In one embodiment, the capping layer 36 includes silicon with athickness ranging from about 4 nm to about 7 nm. The EUV mask 18 mayfurther include a buffer layer 38 disposed above the capping layer 36 toserve as an etching-stop layer in a patterning or repairing process ofan absorption layer, which will be described later. The buffer layer 38has different etching characteristics from the absorption layer disposedthereabove. The buffer layer 38 includes ruthenium (Ru), Ru compoundssuch as RuB, RuSi, chromium (Cr), chromium oxide, and chromium nitridein various examples.

The EUV mask 18 also includes an absorber layer 40 (also referred to asan absorption layer) formed over the buffer layer 38. In someembodiments, the absorber layer 40 absorbs the EUV radiation directedonto the mask 18. In various embodiments, the absorber layer may be madeof tantalum boron nitride (TaBN), tantalum boron oxide (TaBO), orchromium (Cr), Radium (Ra), or a suitable oxide or nitride (or alloy) ofone or more of the following materials: Actinium, Radium, Tellurium,Zinc, Copper, and Aluminum.

FIG. 3 is a diagrammatic fragmentary cross-sectional side view of asemiconductor wafer 45 in accordance with various aspects of the presentdisclosure. The semiconductor wafer 45 may include an integrated circuit(IC) chip, system on chip (SoC), or portion thereof, and may includevarious passive and active microelectronic devices such as resistors,capacitors, inductors, diodes, metal-oxide semiconductor field effecttransistors (MOSFET), complementary metal-oxide semiconductor (CMOS)transistors, bipolar junction transistors (BJT), laterally diffused MOS(LDMOS) transistors, high power MOS transistors, or other types oftransistors.

Referring to FIG. 3 , a semiconductor wafer 45 includes a substrate 48.In some embodiments, the substrate 48 is a silicon substrate doped witha p-type dopant such as boron (for example a p-type substrate).Alternatively, the substrate 48 could be another suitable semiconductormaterial. For example, the substrate 48 may be a silicon substrate thatis doped with an n-type dopant such as phosphorous or arsenic (an n-typesubstrate). The substrate 48 could include other elementarysemiconductors such as germanium and diamond. The substrate 48 couldoptionally include a compound semiconductor and/or an alloysemiconductor. Further, the substrate 48 could include an epitaxiallayer (epi layer), may be strained for performance enhancement, and mayinclude a silicon-on-insulator (SOI) structure.

In some embodiments, the substrate 48 is substantially conductive orsemi-conductive. The electrical resistance may be less than about 10³ohm-meter. In some embodiments, the substrate 48 contains metal, metalalloy, or metal nitride/sulfide/selenide/oxide/silicide with the formulaMXa, where M is a metal, and X is N, S, Se, O, Si, and where “a” is in arange from about 0.4 to 2.5. For example, the substrate 48 may containTi, Al, Co, Ru, TiN, WN2, or TaN.

In some other embodiments, the substrate 48 contains a dielectricmaterial with a dielectric constant in a range from about 1 to about 40.In some other embodiments, the substrate 48 contains Si, metal oxide, ormetal nitride, where the formula is MXb, wherein M is a metal or Si, andX is N or O, and wherein “b” is in a range from about 0.4 to 2.5. Forexample, the substrate 48 may contain SiO₂, silicon nitride, aluminumoxide, hafnium oxide, or lanthanum oxide.

A material layer 50 is formed over the substrate 48. The material layer50 can be patterned via a lithography process and as such may also bereferred to as a patternable layer. In an embodiment, the material layer50 includes a dielectric material, such as silicon oxide or siliconnitride. In another embodiment, the material layer 50 includes metal. Inyet another embodiment, the material layer 50 includes a semiconductormaterial.

In some embodiments, the material layer 50 has different opticalproperties than photoresist. For example, the material layer 50 has adifferent n, k, or T value from photoresist. In some embodiments, thematerial layer 50 comprises at least one of different polymer structure,acid labile molecule, PAG (photo acid generator), quencher, chromophore,cross linker, or solvent, which lead to different n value tophotoresist. In some embodiments, the material layer 50 and photoresisthave different etching resistance. In some embodiments, the materiallayer 50 contains an etching resistant molecule. The molecule includeslow onishi number structure, double bond, triple bond, silicon, siliconnitride, Ti, TiN, Al, aluminum oxide, SiON, or combinations thereof.

It is understood that the substrate 48 and the material layer 50 mayeach include additional suitable material compositions in otherembodiments.

A photoresist layer 60 is formed over the material layer 50. In theembodiment shown in FIG. 3 , the photoresist layer 60 includes apositive photoresist, but it is understood that the photoresist layer 60may be a negative photoresist in alternative embodiments. Thephotoresist layer 60 may be formed by a spin-coating process. Thephotoresist layer 60 contains components such as a polymer, photo acidgenerators (PAG), quenchers, chromophore, surfactant, cross linker, etc.In an embodiment, the photo acid generator is bonded to the polymer. Ina subsequent photolithography process, photons induce decomposition ofthe PAG. As a result, a small amount of acid is formed, which furtherinduces a cascade of chemical transformations in the photoresist layer60. The photoresist layer 60 may also optionally include a quencher thatis disposed within the photoresist layer 60 in order to improve criticaldimension (CD) control.

The photoresist layer 60 contains a photo-acid generator (PAG). In someembodiments, the photo-acid generator includes an acid generatorcomponent and a sensitizer component. The sensitizer component is alsoreferred to as a sensitizer moiety, and it is bonded or linked to theacid generator through a linker.

In some embodiments, the photoresist layer 60 may be a tri-layerphotoresist. A tri-layer photoresist may include a bottom layer (alsoreferred to as an under layer), a middle layer, and a top layer (the toplayer may also be referred to as a PR layer). In some embodiments, thebottom layer includes a CxHyOz material, the middle layer includes aSiCxHyOz material, and the top layer includes a CxHyOz material. TheCxHyOz material of the bottom layer may be identical to the CxHyOzmaterial of the top layer in some embodiments, but they may also bedifferent in other embodiments. The top layer also includes aphoto-sensitive element, such as a photo-acid generator (PAG). Thisallows a photolithography process to be performed to pattern the toplayer. Typically, the top layer is patterned by a photolithographyprocess, which may include one or more exposure, baking, developing, andrinsing processes (not necessarily performed in this order). Thephotolithography process patterns the top layer into a photoresist mask,which may have one or more trenches or openings that expose the middlelayer therebelow. The middle layer is then etched using the photoresistmask to form a patterned middle layer, and the bottom layer is thenetched using the patterned middle layer to form a patterned bottomlayer. The patterned bottom layer is then used to pattern the variouslayers below.

As discussed above, photon absorption has been a problem in EUVlithography if conventional organic photoresist is used. Therefore, thephotoresist layer 60 shown in FIG. 3 has metal-containing (ormetal-compound-containing) material 70 added therein. In someembodiments, the metal-containing material 70 includes Caesium (Cs),Barium (Ba), Lanthanum (La), Indium (In), Cerium (Ce), Siliver (Ag), orTin (Sn), or combinations or compounds thereof. In embodiments where thephotoresist layer 60 is a tri-layer photoresist, the metal-containingmaterial 70 may be located in any one of the bottom layer, the middlelayer, the top layer, or in all of these layers.

The metal-containing material 70 helps enhance the photon absorption inEUV lithography. However, as discussed above, the metal-containingmaterial 70 may cause contamination problems. Therefore, the presentdisclosure will remove the metal-containing particles after (or during)the photoresist layer 60 has been used to perform EUV lithographypatterning.

FIG. 4 illustrates a flow of cleaning the wafer 45 to remove thecontaminant metal-containing material 70 according to an embodiment ofthe present disclosure. As is shown in FIG. 4 , a material 80 isdispensed on the wafer 45. The material 80 may include a photoresistspecifically configured for EUV lithography, which as discussed aboveincludes a metal-containing material such as the metal-containingmaterial 70 shown in FIG. 3 . The material 80 may also include adeveloper solution that is used to develop the photoresist.

A cleaning fluid 100 is applied to the wafer 45 to remove themetal-containing material 70. The cleaning fluid 100 is applied to aback side of the wafer 45 and/or the side edges of the wafer 45. This isbecause the wafer transferring process (e.g., as the wafer 45 istransferred out of the one semiconductor fabrication tool to anothersemiconductor fabrication tool) may involve physical contact with theback side or the side edges of the wafer 45. For example, as the wafer45 is transferred out of a semiconductor fabrication tool (which may bea EUV lithography apparatus in an embodiment), various components of thesemiconductor fabrication tool may come into contact with the bottom(e.g., back side) or side portions of the wafer 45. Through suchcontact, the metal-containing material 70 (FIG. 3 ) may be left on thesemiconductor fabrication tool. If a subsequent process performed bythat semiconductor fabrication tool is supposed to be metal-free, thenthe metal-containing material 70 may be considered a contaminant.

As another example, if the metal-containing material 70 is notthoroughly cleaned off of the wafer 45, the metal-containing material 70may contaminate a new semiconductor fabrication tool as the wafer isloaded into the new semiconductor fabrication tool. This may beexacerbated by various heating processes, which facilitate the escape ofthe metal-containing material 70 from the wafer 45. The new (and nowcontaminated) semiconductor fabrication tool may be intended to performa semiconductor fabrication process in a metal-free environment, inwhich case the presence of the metal-containing material 70 therein isundesirable. For these reasons, the metal-containing material 70 iscleaned off using the cleaning fluid 100. To enhance the effectivenessof the cleaning, the cleaning fluid 100 is configured to mostly targetthe back side and the side edges of the wafer 45, although the frontside of the 45 may be optionally cleaned as well.

The material compositions of the cleaning fluid 100 are carefullyconfigured to enhance the removal of the metal-containing material 70from the wafer 45. For example, the cleaning fluid 100 contains asolvent that is selected to have specific ranges with respect to Hansensolubility parameters of delta D, delta P, and delta H. Hansensolubility parameters provide a way to predict whether one material willdissolve in another and form a solution. A molecule of a given materialhas three Hansen parameters (each generally measured in MPa^(0.5)) deltaD, delta P, and delta H. Delta D is the energy from dispersion forcesbetween molecules. Delta P is the energy from dipolar intermolecularforce between molecules. Delta H is the energy from hydrogen bondsbetween molecules. These three delta parameters may be viewed ascoordinates for a point in a three-dimensional “Hansen space”. Thenearer two molecules are in this three-dimensional “Hansen space”, themore likely they are to dissolve into each other.

According to the various aspects of the present disclosure, the solventis configured to have specific ranges of Hansen parameters so that themetal-containing material 70 can be easily dissolved and consequentlyremoved. In some embodiments, the solvent's Hansen parameters are suchthat a delta D is in a range from 13 to 25, a delta P is in a range from3 to 25, and a delta H is in a range from 4 to 30. In some otherembodiments, the solvent's Hansen parameters are such that a delta D isin a range from 15 to 22, a delta P is in a range from 3.5 to 17, and adelta H is in a range from 5 to 16.

In some embodiments, the solvent is an aqueous solvent. A water-solubleacid or water-soluble base may be added to the aqueous solvent toenhance the ability of the solvent in removing the metal-containingmaterial 70. The concentration of the acid or base in the aqueoussolvent may be in a range from 0.001% to 30%, for example in a rangebetween 0.1% and 20%. In some embodiments, the concentration of the acidor base in the aqueous solvent is in a range from 0.1% to 10%. If anacid is used, a pka (acid dissociation constant, also referred to anacidity constant or acid-ionization constant, which is a logarithmicvalue herein) of the acid is in a range from −11 to 4, for example from−11 to 3. Non-limiting examples of the aqueous acid may include H₂SO₄,HNO₃, HCl, H₃PO₄, CCl₃COOH, HBr, or combinations thereof. If a base isused, the pka of the base is in a range from 9 to 40, for example from10-20. Non-limiting examples of the aqueous base may include NaOH, NH₃,KOH, TMAH, TEAH, or combinations thereof. In some embodiments, a metalchelate may be added to the aqueous solvent addition to, or instead of,the acid or base. In these embodiments, the concentration of the metalchelate in the aqueous solvent may be in a range from 0.001% to 30%, forexample in a range between 0.1% and 20%. Non-limiting examples of themetal chelate may include ethylenediaminetetraacetic acid (EDTA),ethylenediamine-N, N′-disuccinic acid (EDDS),diethylenetriaminepentaacetic acid (DTPA), polyaspartic acid, trans-1,2-Cyclohexanediamine-N, N, N′, N′-tetraacetic acid monohydrate,ethylenediamine, or combinations thereof. In some embodiments, theaqueous solvent may also be heated to increase the cleaning efficiency.In some embodiments, the aqueous solvent is heated in a temperatureranging between room temperature (e.g., 25 degrees Celsius) and 75degrees Celsius, for example between 45 and 75 degrees Celsius. In someembodiments, surfactants may also be added to the aqueous solvent toincrease the solubility and/or to reduce the surface tension on thewafer 45. The concentration of the surfactant in the aqueous solvent maybe in a range from 0.1% to 5%. It is understood that the various rangesthe materials discussed herein are configured to enhance the efficacy ofthe solvent, for example the efficacy with respect to cleaning themetal-containing material 70 off of the wafer 45.

In some embodiments, the solvent is an organic solvent. The organicsolvent may have a polar function, such as —OH, —COOH, —CO—, —O—, —COOR,—CN—, —SO—, as non-limiting examples. In various embodiments, theorganic solvent may include PGME, PGEE, GBL, CHN, EL, Methanol, Ethanol,Propanol, n-Butanol, Acetone, DMF, Acetonitrile, IPA, THF, Acetic acid,or combinations thereof. An organic acid or organic base may be added tothe organic solvent to enhance the ability of the solvent in removingthe metal-containing material 70. The concentration of the acid or basein the organic solvent may be in a range from 0.001% to 30%, for examplein a range between 0.1% and 20%. If an acid is used, a pka (aciddissociation constant, also referred to an acidity constant oracid-ionization constant, which is a logarithmic value herein) of theacid is in a range from −11 to 4. Non-limiting examples of the organicacid may include ethanedioic acid, methanoic acid, 2-hydroxypropanoicacid, 2-hydroxybutanedioic acid, citric acid, uric acid,trifluoromethanesulfonic acid, benzenesulfonic acid, ethanesulfonicacid, methanesulfonic acid, oxalic acid dihydrate, maleic acid, orcombinations thereof.

If a base is used, the pka of the base is in a range from 9 to 40.Non-limiting examples of the organic base may include monoethanolamine,monoisopropanolamine, 2-amino-2-methyl-1-propanol, 1H-benzotriazole, 1,2, 4-triazole, 1, 8-diazabicycloundec-7-ene, or combinations thereof. Insome embodiments, a metal chelate may be added to the organic solventaddition to, or instead of, the acid or base. In these embodiments, theconcentration of the metal chelate in the organic solvent may be in arange from 0.001% to 30%. Non-limiting examples of the metal chelate mayinclude ethylenediaminetetraacetic acid (EDTA), ethylenediamine-N,N′-disuccinic acid (EDDS), diethylenetriaminepentaacetic acid (DTPA),polyaspartic acid, trans-1, 2-Cyclohexanediamine-N, N, N′,N′-tetraacetic acid monohydrate, ethylenediamine, or combinationsthereof. In some embodiments, the organic solvent may also be heated toincrease the cleaning efficiency. In some embodiments, the organicsolvent is heated in a temperature ranging between room temperature(e.g., 25 degrees Celsius) and 75 degrees Celsius. In some embodiments,surfactants may also be added to the organic solvent to increase thesolubility and/or to reduce the surface tension on the wafer 45. Theconcentration of the surfactant in the organic solvent may be in a rangefrom 0.1% to 5%. It is understood that the various ranges the materialsdiscussed herein are configured to enhance the efficacy of the solvent,for example the efficacy with respect to cleaning the metal-containingmaterial 70 off of the wafer 45.

FIGS. 5-6 illustrate a flow of cleaning the wafer 45 to remove thecontaminant (e.g., the metal-containing material 70) according to analternative embodiment of the present disclosure. For reasons ofconsistency and clarity, similar components appearing in FIGS. 4-6 arelabeled the same. As is shown in FIG. 5 , the material 80 is dispensedon the wafer 45. As discussed above with reference to FIG. 4 , thematerial 80 may include a metal-containing photoresist specificallyconfigured for EUV lithography (for better photon absorption), and/or itmay also include a developer solution. While the material 80 is appliedon the wafer 45, the cleaning fluid 100 is not applied yet.

Referring now to FIG. 6 , the cleaning fluid 100 is applied to the wafer45 to remove the metal-containing material 70. The cleaning fluid 100 ismostly applied to a back side of the wafer 45 and/or the side edges ofthe wafer 45, and may be optionally applied to the front side of thewafer 45 in some embodiments. As discussed above with reference to FIG.4 , the cleaning fluid 100 includes an aqueous or organic solvent havinga particular range of Hansen solubility parameters to facilitate theremoval of the metal-containing material 70. Various additives such asacid, base, or metal chelate may also be added to the solvent asdiscussed above, to further enhance the efficacy of the cleaning fluid100 in removing the metal-containing material 70. Thus, whereas the flowcorresponding to FIG. 4 is configured to remove the metal-containingmaterial 70 as the metal-containing material 70 is being dispensed (inthe photoresist), the flow corresponding to FIGS. 5-6 is configured toremove the metal-containing material 70 via an extra cleaning step.

Referring now to FIG. 7 , an embodiment of a cleaning system 150 isillustrated. In some embodiments, the cleaning system 150 may be a partof an existing semiconductor fabrication apparatus, for example it maybe integrated into an EUV lithography tool where metal-containingphotoresist is used for EUV lithography. In other embodiments, thecleaning system 150 may be a part of other types of semiconductorfabrication equipment where metal contaminants may be introduced. In theembodiment shown in FIG. 7 , the material 80 (e.g., a metal-containingEUV photoresist and/or a developer solution) is dispensed on the frontside of the wafer 45. The metal in the material 80 may be considered acontaminant and will be removed by the cleaning system 150, as discussedbelow.

The cleaning system 150 includes a chamber 160 in which the wafer 45 isdisposed. In some embodiments, the chamber is sealable so as to isolatethe wafer 45 from other potential contaminants outside the chamber 160.The cleaning system 150 may also include one or more exhaust mechanisms170 that are coupled to the chamber 160 such that fluids (e.g., air,which may include contaminant particles) from inside the chamber 160 maybe “sucked” out of the chamber 160. In other words, a negative pressureis applied to the exhaust mechanisms 170 to create at least a partialvacuum inside or near the exhaust mechanisms 170. The negative pressureapplied to the exhaust mechanisms 170 will force the fluids such as airinside the chamber 160 to flow toward, and then out of, the exhaustmechanisms 170.

The cleaning system 150 further includes a plurality of nozzles 180 and181 that are each configured to spray the cleaning fluid 100 discussedabove with reference to FIGS. 4-6 . In more detail, the nozzle 180 ispositioned below the wafer 45 and is therefore configured to spray thecleaning fluid 100 onto the back side of the wafer 45. The nozzle 181 ispositioned near a side edge of the wafer 45 and is therefore configuredto spray the cleaning fluid 100 onto the side edge of the wafer 45.

It is understood that although two nozzles 180-181 are illustratedherein to spray the cleaning fluid 100, the cleaning system 150 mayinclude other nozzles that are also configured to spray the cleaningfluid 100 onto the wafer 45. For example, more than one nozzle may bepositioned below the wafer 45, more than one nozzle may be positionedaround different side edge points of the wafer 45, and one or morenozzles may also be positioned above the wafer 45 to spray the cleaningfluid 100 onto the front side of the wafer 45. In any case, the cleaningfluid 100 sprayed by the nozzles 180-181 (and other similar nozzles)herein will wash the metal-containing material 70 away from the wafer45, for example away from the back surface and the side surfaces of thewafer 45.

To facilitate the removal of the metal-containing material 70 from thewafer 45, the cleaning system 150 also includes nozzles 190 and 191 thatare each configured to deliver a suitable purging fluid 200 (e.g., air)to the wafer 45. In more detail, the nozzle 190 is positioned below thewafer 45 and is therefore configured to apply the purging fluid 200 ontothe back side of the wafer 45. The nozzle 191 is positioned near a sideedge of the wafer 45 and is therefore configured to spray the purgingfluid 200 onto the side edge of the wafer 45. Positive pressure isapplied through the nozzles 190-191 to ensure that the purging fluid 200spurts out of the nozzles 190-191 and makes contact with the wafer 45.In some embodiments, a magnitude (or absolute value) of the positivepressure applied through the nozzles 190-191 exceeds the magnitude (orabsolute) value of the negative pressured applied through the nozzles180-181. In some embodiments, the purging fluid 200 includes clean dryair (CDA). In other embodiments, the purging fluid 200 includesnitrogen. In yet other embodiments, the purging fluid 200 includesanother suitable material that does not react with films on the wafer45.

The interaction between the purging fluid 200 and the wafer enhances theeffectiveness of the washing or the removal of contaminant particles,including the removal of the metal-containing material 70. In thismanner, the nozzles 190-191 “pushes”, and the exhaust mechanisms 170“pulls” the metal containing-material 70 off of the wafer 45 and out ofthe chamber 160.

It is understood that although two nozzles 190-191 are illustratedherein to deliver the purging fluid 200, the cleaning system 150 mayinclude other nozzles that are also configured to deliver the purgingfluid 200 onto the wafer 45. For example, more than one nozzle may bepositioned below the wafer 45, more than one nozzle may be positionedaround different side edge points of the wafer 45, and one or morenozzles may also be positioned above the wafer 45 to deliver the purgingfluid 200 onto the front side of the wafer 45. In some embodiments, arespective purging fluid nozzle (e.g., nozzles 190-191) is locatedadjacent to a respective cleaning fluid nozzle (e.g., nozzles 180-181).In any case, the purging fluid 200 delivered by the nozzles 190-191 (andother similar nozzles) herein will help wash the metal-containingmaterial 70 away from the wafer 45, for example away from the backsurface and the side surfaces of the wafer 45.

In addition to implementing the cleaning fluid nozzles 180-181 and thepurging fluid nozzles 190-191, the cleaning system 150 also hasmechanisms in place to spin the wafer 45 during the cleaning process,such as during the application of the cleaning fluid 100 and/or thepurging fluid 200. For example, the cleaning system 150 may include aspinner apparatus 250. The spinner apparatus 250 may include a chuck, apedestal, and/or a motor. The spinner apparatus is mechanically coupledto the wafer 45, and it is configured to rotate or spin in a clockwiseand/or a counterclockwise manner. Thus, as the spinner apparatus 250rotates or spins, so does the wafer 45.

To control the spin of the spinner apparatus 250, the cleaning system150 may include a controller 300 that is communicatively coupled to thespinner apparatus 250. The controller 300 may be remotely located (orlocally located) from the rest of the cleaning system 150. In otherwords, the controller 300 may be implemented outside the chamber 160 insome embodiments, and it may be implemented inside the chamber 160 inother embodiments. The controller 300 may also be a part of an overallsemiconductor manufacturing system, of which the cleaning system 150 isa part. The controller 300 may include electronic memory and one or moreelectronic processors configured to execute programming instructionsstored in the electronic memory, which may involve a program controllingthe spin of the spinner apparatus 250. The controller 300, based on theprogram, controls the spinner apparatus (and therefore the wafer 45) torotate or spin according to a specific spin speed, spin duration, and/ora spin direction (e.g., clockwise or counterclockwise). In someembodiments, the controller 300 is configured to set a spin rate/speedof the wafer in a range between about 800 RPM to about 4500 RPM, forexample between about 800 RPM and about 3500 RPM. This range of the spinspeed is optimized to enhance the distribution of the cleaning fluid 100on the wafer 45 and to facilitate the removal of the contaminantmaterials such as the metal-containing material 70.

It is understood that the spinning of the wafer 45 need not be only inone direction. Instead of performing the spin in just a clockwisedirection or just in a counterclockwise direction, the wafer 45 (underthe control of the controller 300) may undergo a combination ofclockwise and counterclockwise spins. For example, the wafer 45 may beconfigured to spin in a clockwise direction for an X number of seconds,followed by a spin in the counterclockwise direction for a Y number ofseconds (where Y may be the same as X or may be different), or viceversa. The combination of performing clockwise spins andcounterclockwise spins in an alternating manner may further enhance theapplication of the cleaning fluid 100 and the purging fluid 200 withrespect to the wafer 45, thereby improving the removal of themetal-containing materials as contaminants.

FIG. 8 provides a visual illustration of a flow in which the cleaningprocess is performed according to embodiments of the present disclosure.Referring to FIG. 8 , an example lithography process 400 is illustrated.In some embodiments, the lithography process 400 is an EUV lithographyprocess. The lithography process 400 includes a step 410 in which aphoto-sensitive material is coated onto a wafer such as the wafer 45.The photo-sensitive material may include a tri-layer photoresist(including a top layer (PR), a middle layer (ML), and an under layer(UL)). The photo-sensitive material may be coated via a spin-coatingprocess. As discussed above, to enhance the photon absorption, thephoto-sensitive material contains metal, which are consideredcontaminants after the lithography process is performed and should beremoved.

The lithography process 400 includes a step 420 of pre-exposure baking,in which the wafer (and the metal-containing photo-sensitive materialcoated thereon) is baked. The lithography process 400 includes a step430 of exposure, in which the wafer (and the metal-containingphoto-sensitive material coated thereon) is exposed. In someembodiments, the exposure involves using ultraviolet (UV) light or usinge-beam to expose the wafer 45. The lithography process 400 includes astep 440 of post-exposure bake, in which the wafer 45 (and themetal-containing photo-sensitive material coated thereon) is baked. Thelithography process 400 includes a step 450 of developing, in which thewafer (and the metal-containing photo-sensitive material coated thereon)is developed via an application of a developer solution onto the wafer.It is understood that the lithography process 400 may include additionalprocesses that are not specifically illustrated or discussed herein.

According to the process flow in FIG. 8 , the wafer 45 is cleaned, usingthe cleaning system 150 discussed above with reference to FIG. 7 , whilethe steps 410 and 450 are performed. In other words, as themetal-containing photo-sensitive material is applied to the wafer 45,the wafer 45 is cleaned using the cleaning system 150. In addition, asthe developed solution is applied to the wafer 45 to develop the exposedphoto-sensitive material, the wafer 45 is also cleaned using thecleaning system 150. It is understood, however, that according to thisprocess flow, the wafer 45 need not necessarily be cleaned twice. Forexample, the wafer 45 may be cleaned just during the step 410, oralternatively it may be cleaned just during the step 450, but notnecessarily during both steps 410 and 450.

FIG. 9 provides another visual illustration of another flow in which thecleaning process is performed according to embodiments of the presentdisclosure. For reasons of consistency and clarity, similar elementsappearing in FIGS. 8-9 are labeled the same. In comparison to theprocess flow shown in FIG. 8 , the process flow shown in FIG. 9 performsthe wafer cleaning after the steps 410, 420, 440, and 450, rather thanduring the steps 410 and 450. In other words, the wafer 45 may becleaned (using the cleaning system 150) after the metal-containingphoto-sensitive material has been coated onto the wafer, and/or afterthe pre-exposure baking process, and/or after the post-exposure bakingprocess, and/or after the developing process. Again, it is understoodthat the wafer 45 need not necessarily be cleaned four times in thisprocess flow. For example, the wafer 45 may be cleaned (using thecleaning system 150) just after any one of the steps 410, 420, 440, and450, or combinations thereof.

It is understood that although the discussions above have focused oncleaning the wafer to remove a metal contaminant arising from ametal-containing EUV photoresist, the systems and method discussedherein is not limited to this particular context. The systems andmethods of the present disclosure can also be used in othersemiconductor fabrication situations where metal may be considered acontaminant and needs to be removed.

It is also understood that an additional step of rinsing the wafer witha high-contact-angle material may be optionally performed in someembodiments. This is diagrammatically illustrated in FIG. 10 , whichillustrates several different process flows according to embodiments ofthe present disclosure. Referring to FIG. 10 , a flow A includes a step510 of performing a high-contact-angle material rinsing process to thewafer, for example the wafer 45 discussed above. The rinse may beapplied to a backside or an edge of the wafer. The high-contact-anglematerial may include a material that has a contact angle that is greaterthan 75% with respect to water. After the wafer surface is treated withthe high-contact-angle material, the wafer surface becomes hydrophobic.Since this is done before the photoresist layer is coated on the wafersurface, it makes the subsequent wafer cleaning easier. In other words,the hydrophobicity of the wafer surface (due to the application of thehigh-contact-angle material in step 510) allows the metal-containingmaterial in the photoresist to be more easily washed off of the wafer.

Still referring to FIG. 10 , a step 520 is performed after thehigh-contact-angle material rinse step of 510. In step 520, a metallicfilm is dispensed. The metallic film may be the metal-containingmaterial in the photoresist discussed above. Thus, step 520 may involvecoating a metal-containing photoresist material on the wafer surface.

A step 530 is performed after the step 520. The step 530 involves a newsolvent rinsing process, The new solvent may be embodiments of thecleaning fluid 100 discussed above, for example containing a solventwith the specified ranges of Hansen parameters. Again, the step 530allows the metal-containing material to be washed off of the wafer,which reduces risks of contamination.

Flows B and C are similar to flow A. In flows B and C, another step 540is performed, in which a commercial solvent rinsing process is performedto the wafer. In some embodiments, the commercial solvent may includeother commonly used solvents in the industry in a photolithographyprocess. The difference between flows B and C is that, the step 540(commercial solvent rinsing) is performed after the step 530 in flow B,but it is performed before the step 530 in flow C.

Regardless of the specific flow, it is understood that the optional step510 of rinsing the wafer with the high-contact-angle material willfacilitate the cleaning process discussed above. In some embodiments,the high-contact-angle material includes a carbon fluoride compound, forexample a C_(x)F_(y) unit. In various embodiments, x is in a rangebetween 1 and 7, and y is saturated by structure. This carbon fluoridecompound may be in the form of an additive that is added to a solvent.In some embodiments, the carbon fluoride compound is a polymer. Thecarbon fluoride compound may be branched in some embodiments, butunbranched in other embodiments. The carbon fluoride compound may alsobe cyclic in some embodiments, but uncyclic in other embodiments. Insome embodiments, the carbon fluoride compound may be saturated withhydrogen or halogen atom.

In embodiments where the carbon fluoride compound is a polymer, thepolymer chain may include polystyrene, acrylate, or a 1˜10 carbon unitto form a polymer. The polymer may be within a C_(x)F_(y) monomer.

FIG. 11 is a flowchart of a method 600 of performing a semiconductorfabrication process according to various aspects of the presentdisclosure.

The method 600 includes a step 610 of forming a patternable layer over asubstrate. In some embodiments, the substrate is substantiallyconductive or semi-conductive. The electrical resistance may be lessthan about 103 ohm-meter. In some embodiments, the substrate containsmetal, metal alloy, or metal nitride/sulfide/selenide/oxide/silicidewith the formula MXa, where M is a metal, and X is N, S, Se, O, Si, andwhere “a” is in a range from about 0.4 to 2.5. For example, thesubstrate 48 may contain Ti, Al, Co, Ru, TiN, WN₂, or TaN. In some otherembodiments, the substrate contains a dielectric material with adielectric constant in a range from about 1 to about 40. In some otherembodiments, the substrate contains Si, metal oxide, or metal nitride,where the formula is MXb, wherein M is a metal or Si, and X is N or O,and wherein “b” is in a range from about 0.4 to 2.5. For example, thesubstrate may contain SiO₂, silicon nitride, aluminum oxide, hafniumoxide, or lanthanum oxide.

The patternable layer formed over the substrate has different opticalproperties than photoresist. For example, the patternable layer has adifferent n, k, or T value from photoresist. In some embodiments, thelayer comprises at least one of different polymer structure, acid labilemolecule, PAG (photo acid generator) loading, quencher loading,chromophore, cross linker, or solvent, which lead to different n valueto photoresist. In some embodiments, the patternable layer andphotoresist have different etching resistance. In some embodiments, thepatternable layer contains an etching resistant molecule. The moleculeincludes low onishi number structure, double bond, triple bond, silicon,silicon nitride, Ti, TiN, Al, aluminum oxide, SiON, or combinationsthereof.

The method 600 includes a step 620 of coating a photoresist layer overthe patternable layer. The photoresist layer includes a metal-containingmaterial.

The method 600 includes a step 630 of performing a lithography processto the photoresist layer to form a patterned photoresist. In someembodiments, the lithography process includes an extreme ultraviolet(EUV) lithography process.

The method 600 includes a step 640 of cleaning the wafer with a cleaningfluid to remove the metal-containing material. In some embodiments, thecleaning fluid includes a solvent having Hansen solubility parameters ofdelta D in a range between 13 and 25, delta P in a range between 3 and25, and delta H in a range between 4 and 30. In some embodiments, thesolvent is an aqueous solvent. In some embodiments, the solvent is anorganic solvent. In some embodiments, the solvent contains an acid withan acid dissociation constant (pka) less than 4, for example between −11and 4. In some embodiments, the solvent contains a base with an aciddissociation constant (pka) greater than 9, for example between 9 and40. In some embodiments, the solvent contains a metal chelate. In someembodiments, the solvent contains a surfactant. In some embodiments, thesolvent is heated to a temperature ranging between room temperature and75 degrees Celsius. In some embodiments, the cleaning the wafercomprises spinning the wafer as the wafer is being cleaned.

In some embodiments, the cleaning the wafer comprises applying thecleaning fluid to at least one of: a back side of the wafer or a sideedge of the wafer. In some embodiments, the cleaning the wafer comprisesdelivering a purging fluid to the wafer, the purging fluid beingdelivered to at least one of: a back side of the wafer or a side edge ofthe wafer. In some embodiments, the performing the lithography processincludes performing: a photoresist-coating process, a pre-exposurebaking process, an exposure process, a post-exposure baking process, anda developing process. The cleaning the wafer may be performed while thephotoresist-coating process or the developing process is performed. Thecleaning the wafer may also be performed: after the photoresist-coatingprocess, after the pre-exposure baking process, after the post-exposurebaking process, or after the developing process.

It is understood that additional processes may be performed before,during, or after the steps 610-640 of the method 600 to complete thefabrication of the semiconductor device. For reasons of simplicity,these additional steps are not discussed herein in detail.

Based on the above discussions, it can be seen that the presentdisclosure offers advantages over conventional methods. It isunderstood, however, that other embodiments may offer additionaladvantages, and not all advantages are necessarily disclosed herein, andthat no particular advantage is required for all embodiments. Oneadvantage is that the photoresist material herein offers improvedlithography performance, for example better photon absorptionperformance due to the presence of metal or metal compounds in thephotoresist. Another advantage is that the systems and methods ofcleaning the wafer (e.g., using the novel solvent herein as a cleaningfluid to wash the metal-containing material off the wafer) reducecontamination caused by the metal-containing material, for both theapparatus in which the lithography process is performed, and also forother semiconductor fabrication tools to which the wafer (after beingcleaned) is transferred. For at least these reasons, the presentdisclosure improves semiconductor fabrication performance.

One aspect of the present disclosure pertains to a method of fabricatinga semiconductor device. A photoresist layer is coated over a wafer. Thephotoresist layer includes a metal-containing material. A lithographyprocess is performed to the photoresist layer to form a patternedphotoresist. The wafer is cleaned with a cleaning fluid to remove themetal-containing material.

Another aspect of the present disclosure pertains to a method offabricating a semiconductor device. A photoresist layer is coated over awafer. The photoresist layer includes a metal-containing material. Anextreme ultraviolet (EUV) lithography process is performed to thephotoresist layer to form a patterned photoresist. The wafer is cleanedwith a cleaning fluid to remove the metal-containing material. Thecleaning fluid includes a solvent having Hansen solubility parameters ofdelta D in a range between 13 and 25, delta P in a range between 3 and25, and delta H in a range between 4 and 30. The solvent contains anacid with an acid dissociation constant less than 4 or a base with anacid dissociation constant greater than 9.

Yet another aspect of the present disclosure pertains to a system offabricating a semiconductor device. The system includes a chamberconfigured to coat a metal-containing photoresist material onto a waferas a part of an EUV lithography process. The system includes one or morefirst nozzles configured to apply a cleaning fluid to the wafer. Thecleaning fluid has a material composition configured for removing ametal contaminant from the wafer. The metal contaminant arises from themetal-containing photoresist material. The system includes one or moresecond nozzles configured to apply a purging fluid to the wafer. Thepurging fluid facilitates a removal of the metal contaminant from thewafer.

The foregoing has outlined features of several embodiments so that thoseskilled in the art may better understand the detailed description thatfollows. Those skilled in the art should appreciate that they mayreadily use the present disclosure as a basis for designing or modifyingother processes and structures for carrying out the same purposes and/orachieving the same advantages of the embodiments introduced herein.Those skilled in the art should also realize that such equivalentconstructions do not depart from the spirit and scope of the presentdisclosure, and that they may make various changes, substitutions andalterations herein without departing from the spirit and scope of thepresent disclosure.

What is claimed is:
 1. A method comprising: forming a hydrophobicsurface on a substrate; forming a photosensitive layer on thehydrophobic surface of the substrate, wherein the photosensitive layerincludes a metal-containing material; performing an exposure process onthe photosensitive layer; and after performing the exposure process,removing the metal-containing material.
 2. The method of claim 1,wherein the forming of the hydrophobic surface on the substrate includesapplying a fluoride containing material to the substrate.
 3. The methodof claim 1, wherein the removing of the metal-containing materialincludes spinning the substrate.
 4. The method of claim 1, wherein theremoving of the metal-containing material includes applying a gasmaterial.
 5. The method of claim 4, wherein the gas material includes anitrogen containing material.
 6. The method of claim 1, wherein theremoving of the metal-containing material includes applying a materialthat includes an ingredient selected from the group consisting of anaqueous acid, an organic acid, an aqueous base, an organic base, and ametal chelate.
 7. The method of claim 1, wherein the metal-containingmaterial is selected from the group consisting of Caesium (Cs), Barium(Ba), Lanthanum (La), Indium (In), Cerium (Ce), Silver (Ag) and Tin(Sn).
 8. The method of claim 1, wherein the performing of the exposureprocess on the photosensitive layer includes performing an extremeultraviolet lithography exposure process.
 9. A method comprising:forming a photosensitive layer on a substrate, wherein thephotosensitive layer includes a metal-containing material; performing anexposure process on the photosensitive layer; performing a post-exposurebaking process on the photosensitive layer; after performing thepost-exposure baking process, performing a first removal process toremove a first portion of the metal-containing material; afterperforming the first removal process, developing the exposedphotosensitive layer; and after performing the developing of the exposedphotosensitive layer, performing a second removal process to remove asecond portion of the metal-containing material.
 10. The method of claim9, wherein the performing of the first removal process to remove thefirst portion of the metal-containing material includes applying apurging gas to the substrate.
 11. The method of claim 10, wherein theperforming of the first removal process to remove the first portion ofthe metal-containing material includes applying a first cleaning fluid,and wherein the cleaning fluid and the purging gas are different fromeach other.
 12. The method of claim 9, wherein the performing of thefirst removal process to remove the first portion of themetal-containing material includes applying a first cleaning fluid,wherein the developing of the exposed photosensitive layer includesapplying a developer solution, wherein the first cleaning fluid and thedeveloper solution are different from each other.
 13. The method ofclaim 12, wherein the performing of the second removal process to removethe second portion of the metal-containing material includes applying asecond cleaning fluid that is different than the developer solution. 14.The method of claim 9, further comprising forming a hydrophobic surfaceon the substrate prior to forming the photosensitive layer on thesubstrate.
 15. The method of claim 9, wherein the performing of thefirst removal process to remove the first portion of themetal-containing material includes applying a first cleaning fluid, andwherein the first cleaning fluid includes a solvent having Hansensolubility parameters of delta D in a range between 13 and 25, delta Pin a range between 3 and 25, and delta H in a range between 4 and 30.16. A method comprising: providing a substrate having a photosensitivelayer thereon, the photosensitive layer including a metal-containingmaterial; performing an exposure process on the photosensitive layer;and developing the exposed photosensitive layer by a applying adeveloper solution, wherein during the developing of the exposedphotosensitive layer the removal of the metal-containing material occursby applying a purging gas and a cleaning fluid, wherein the developersolution, the cleaning fluid and the purging gas are different from eachother.
 17. The method of claim 16, wherein the cleaning fluid includesan ingredient selected from the group consisting of an aqueous acid, anorganic acid, an aqueous base, an organic base, and a metal chelate. 18.The method of claim 16, wherein the applying of the purging gas and thecleaning fluid includes heating the cleaning fluid.
 19. The method ofclaim 16, wherein the cleaning fluid includes a solvent having Hansensolubility parameters of delta D in a range between 13 and 25, delta Pin a range between 3 and 25, and delta H in a range between 4 and 30,and wherein the cleaning fluid further includes one of an aqueous acidor an organic acid.
 20. The method of claim 16, wherein the cleaningfluid includes a solvent having Hansen solubility parameters of delta Din a range between 13 and 25, delta P in a range between 3 and 25, anddelta H in a range between 4 and 30, and wherein the cleaning fluidfurther includes one of an aqueous base or an organic base.